Resinous compositions as detergent additives



United 7 States Patent O REsrNous eoMrosirioNs as DETERGENT ADDTTHVES' I G eorge li. Touey and Herman E. Davis, KingsportQ'Tenni,

assignors to Eastman Kodak Company, Rochester, N .Y., a corporation of New'liersey t No Drawing. Filed Aug. 1, 1961, Ser. No. 128,382

Claims. (Cl. 252-152) This invention relates to {compositions Containing water-soluble, salts of condensation products of formal- "dehyde with carbamides, amino-azines, or carbamides and 'amino-azines. This invention particularly relates to comwith the fabric or material.

- (2) The soil particles are removed from the fabric and,

I -(3.). A re prevented frombeing redeposited on the cloth.

'Oneobject'o'f our invention is to provide compositions which are-effective in removing soil during the washing of Another .object of our invention is to textile fabrics. proyidecompositions which will, prevent .these removed dirt .or soil particles from redepositing on. the materials being washed. Other objects OfOllI invention will appear herein.

iWe have found that water-soluble sulfonate slats of condensation products oftormaldehyde and a carbamide, an amino-azineora carbamide and an amino-arise are of value in laundering textile fabrics in that they aid in keeping-the soil or dirt particles in suspension in the wash water and thus prevent them from dedepositing on the fabrics being laundered. v

Up to the present time the principal substance which has been disclosed as of value as the suspending agent in i detergents is sodium carboxymethylcellulose. We have found, however, that water-soluble sulfonate salts of condensation products of formaldehyde .with carbamides, amino-azines, and'carbamides and amino-azines are as good as or better than sodium carboxymethylcellulo-se in preventing the depositing of dirt particles onto the mate- I rials being washed.

The condensation products of formaldehyde with a 'carbamide, an amino-azine, or a carbamide and anaminoaz ine may be prepared by procedures known to those The melamine-formaldehyde com-- pound, for example, is preferably prepared under alkaline "conditions, say at a pH of around '8. Each molecule of the condensation product should contain at least three skilled in the art.

units selected from the group consisting of the carbamides and the amino-azines. The carbamides which may be idine, dicyanamide and the like. The amino-azines which may be condensed with formaldehyde include melamine, melam, ammelinc, thioammeline and the like; Mixtures of 3,152,993 Patented Get. 13, 1964 vdehyde with melamine'may contain'from 3 to" 5(), but

preferably ,3 to 30, methylol melamine residue units. 7 Thewater-soluble sulfonate salts of these condensation products, which are used in compositions in accordance with our invention, may be advantageously prepared by reacting the resin with alkali metal metabisulfite, sulfite,

or bisulfite." An average of at least one sulfonate group for each four units of carbamide and/ or amino-azine is desirable. I

Example I will illustrate a method for the preparation of a watensoluble sulfonate salt of a condensation prodnot of formaldehyde with urea.

EXAMPLE I 200 grams .of paraformaldehyde was dissolved in an. alcoholic alkaline solution. consisting of 1134 cc. of ethanol, 66 cc. of water, and 5 'g. of sodium hydroxide. 200 grams of urea was added slowly at room temperature and stirred until a homogeneous solution resulted. The heavy white precipitate which formed after standing for about 2 hours was separated and dried. The precipitate had a melting point of 278- 285 C. with decomposition.

The urea-formaldehyde prccondensate thus :formed was dissolved in 800 ml. of water, heated and adjusted to a pH of 5 with a dilute HCl solution. It was then refluxed until the solution became cluody (approximately 20 minutes). The pH was adjusted to 88.5 using ammonium hydroxide.

homogeneous solution resulted which on cooling to room temperature became viscous and faintly hazy.. The pH 7 was 7.2. The product was precipitated into 2 liters of methanol and stirred'vigorously. The white granular precipitate which formed was removed by filtration and' washed with 1 liter of methanol. The-product was watersoluble which it retainedeven after heating at 100 C. for 16 hours. Analysis for sulfur indicated an average of 1 sodium sulfonate group for each 5 dimethylolurea units. The actiyty of the product as a detergent additive is demonstrated in Table I.

Example II demonstrates a method for the preparation of a Water-solublesulfonate salt of a condensation product of formaldehyde with melamine.

7 EXAMPLE II 126 grams of melamine was slurried in 300 grams of a 30% aqueous formaldehyde solution and the pH of the solution was adjusted to 8.5 by adding 30 ml. of concentrated ammonium hydroxide. The mixture was heated to C. and maintained at this temperature for 1 hour. A clear homogeneous solution was formed. 31 grams of sodium bisulfite was added and the mixture was refluxed condensed with formaldehyde include urea, thiourea, guancarbamides and/or amino-azines may be employed. For 7 ,present purposes, the preferredcarbamide is urea and the preferred aminoazine is melamine. The condensation products of formaldehyde with urea are indicated in the following formula;

V i ii HO CH2[N- o"N-om];.orr wherein 12 may be from 3 to 50 but preferably is from IOto 30. Similarly, thecondensation products of formalfor 1.5 hours; The colorless syrup formed when cooled had a pH of. 9.4. It was slowly poured into 2 liters ofmethanol while stirring vigorously, and the white granular precipitate which formed was removed by filtration and:

Washed with 1 liter of methanol. The white solid was water-soluble which it retained even after heating at i C. for 16 hours. Analysis for sulfur indicated an average of 1 sodium sulfona-te group for each 4 methylol melamine units. The activity of the product as a detergent additive is demonstrated in Table I. P

Tests were run to determine the effectiveness of the detergent additive of our invention in preventing the deposition of soil suspended in water on fabrics therein. In these tests, ,a detergent solution was used which consisted of.0.15% sodium N-methyl-N-oleyl taurate as detergent, 0.05% sodium tripolyphosphate as builder and 99.8%

water. 0.01 gram of each additive to be tested was respectively dissolved in a bottle in a 100 ml. portion of the detergent solution, and 5 cc. of Aqua Black-B (a 35% aqueous suspension of carbon black, manufactured by grams of sodium'bisulfite were added' and the resulting slurry was refluxed for 1.5 hours. A

Binney and Smith Company, New York) was added to each. The detergent-soil solutions were heated to 140 F. for minutes, whereupon a 2" x 2 /2" piece of clean, unsized white cotton cloth was addedv to each bottle. The respective solutions were transferred to standard Launder- O-Meter bottles (pint-size), each containing 10 steel balls, At-inch in diameter. The bottles were sealed and tumbled for 30 minutes at 140 F. in an Atlas Launder-O-Meter. The cloth samples were then removed from the soil solutions, rinsed in warm water,: and dried. Reflectance curves were obtained for each washed cloth with a General Electric Recording Spectrophotometer calibrated against magnesium oxide which is taken as having a reflectance of 100%. In the table below the percent reflectance obtained for four wavelength values in the visible range of spectrum are recorded, for the sample before soiling, and for the samples resulting from the respective washing treatments listed:

. The sulfonated condensation products described are adapted to be mixed with any of the commonly known anionic or non-ionic detergents such as soap, alcohol sulfates, alkyl aryl sulfonates, alkyl sulfonates, sulfated or sulfonated amides, esters and amines,. non-ionic substances and miscellaneous types not readily classified. In general, the additives described may be employed with detergents for use in aqueous systems. The detergent may contain any of the inorganic salts commonly referred to as builders such as sodium sulfate, sodium phosphates, and sodium silicates. The ratio of additive to detergent may vary over a wide range depending on the type of detergent 4 used and the amount of soil which is to be removed from the fabric. Usually, I to 10% detergent additive based on the combined weight of the detergent and builder is sufficient; we prefer to use 15%7 based on the weight of detergent and builder.

Although the invention has been described in considerable detail with reference to certain preferred embodiments thereof, it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

We claim:

1. A composition soluble in water to form a washing solution which is effective not only to remove soil from textile materials but also to minimize redeposition of removed soil comprising the mixture of an organic anionic detergent and a water soluble sulfonate salt of a condensation product of formaldehyde with a compound selected from the group consisting of urea and melamine.

2. The composition of claim 1 wherein the water solublesulfonate salt is the salt of a condensation product of formaldehyde with at least three moles of urea, and contains at least one sulfonate group for each four units of urea. i I

3. The composition of claiml wherein the water soluble sulfonate salt is the salt of a condensation product of formaldehyde with at least three moles of melamine, and contains at least one sulfonate group for each four melamine units.

4. A washing solution which is efiective not'only to remove soil from textile materials but'also to minimize redeposition of removed soil comprising water, an organic anionic detergent, and a water soluble sulfonate salt of a condensation product of formaldehyde with a compound selected from the group consisting of urea and melamine.

5. A process for removing soil from a textile material and minimizing the redeposition of removed soil on the material comprising washing the material with a solution comprising Water, an organc anionic detergent and a water soluble sulfonate salt of a condensation product of formaldehyde with a compound selected from the group consisting of urea and melamine.

References Cited in the fileof this patent Polansky et a1. Sept. 30, 1958 

1. A COMPOSITION SOLUBLE IN WATER TO FORM A WASHING SOLUTION WHICH IS EFFECTIVE NOT ONLY TO REMOVE SOIL FROM TEXTILE MATERIALS BUT ALSO TO MINIMIZE REDEPOSITION OF REMOVED SOIL COMPRISING THE MIXTURE OF AN ORGANIC ANIONIC DETERGENT AND A WATER SOLUBLE SULFONATE SALT OF A CONDENSATION PRODUCT OF FORMALDEHYDE WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF UREA AND MELAMINE. 